US1903299A - Production of artificial materials from cellulose derivatives - Google Patents
Production of artificial materials from cellulose derivatives Download PDFInfo
- Publication number
- US1903299A US1903299A US431966A US43196630A US1903299A US 1903299 A US1903299 A US 1903299A US 431966 A US431966 A US 431966A US 43196630 A US43196630 A US 43196630A US 1903299 A US1903299 A US 1903299A
- Authority
- US
- United States
- Prior art keywords
- acid
- bath
- production
- cellulose derivatives
- solutions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 16
- 229920002678 cellulose Polymers 0.000 title description 15
- 239000001913 cellulose Substances 0.000 title description 12
- 239000012237 artificial material Substances 0.000 title description 9
- 239000002253 acid Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 description 22
- 239000011707 mineral Substances 0.000 description 22
- 150000007513 acids Chemical class 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000001117 sulphuric acid Substances 0.000 description 10
- 235000011149 sulphuric acid Nutrition 0.000 description 10
- 238000007654 immersion Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 238000002166 wet spinning Methods 0.000 description 8
- 229920002301 cellulose acetate Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003086 cellulose ether Polymers 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- NRUQNUIWEUZVLI-UHFFFAOYSA-O diethanolammonium nitrate Chemical compound [O-][N+]([O-])=O.OCC[NH2+]CCO NRUQNUIWEUZVLI-UHFFFAOYSA-O 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
Patented Apr. 4, 1933 UNITED STATES PATENT OFFICE ROBERT PIERCE ROBERTS, REGINALD IVOR REID DEAN, AND LOUIS WILFRED GREGORY,
OF SPONDON, NEAR DERBY, ENGLAND, ASSIGNORS TO CELANESE CORPORATION AMERICA, A CORPORATION OF DELAWARE PRODUCTION or ARTIFICIAL MATERIALS FROM cELLULosE DERIVATIVES No Drawing. Application filed February 27, 1930, Serial No. 431,966, and in Great Britain May 9, 1929.
- This invention relates to the production of artificial filament, threads, ribbons, films and the like by-wet-spinning processes from solutions containing cellulose derivatives, for example cellulose acetate, formate, propionate, butyrate or other carboxylic acid esters or other esters of cellulose, or methyl, ethyl or benzyl cellulose or other cellulose ethers.
According to the present invention filamerits, threads, ribbons, films and the like of good strength may be obtained by extruding solutions of cellulose derivatives into relatively strong mineral acids or acid esters thereof, for example aqueous solutions of sulphuric acid, hydrocholoric acid or phosphoric acid or of ethyl sulphuric acid, mono or di-ethyl phosphoric acid and the like. We find that good spinning may be obtained with relatively strong mineral acids or mineral acid esters and particularly with sulphuric acid solutions, provided that the strength of the solutions be adjusted to avoid a deleterious or undesired degree of hydrolysis of the cellulose ester or ether.
According to a modification of the invention the solutions containing the cellulose derivatives may be extruded into any suitable precipitating bath and thereafter carried into a bath containing relatively strong min-eralacid or acid ester thereof.
The filaments or other products thus obtained or thus treated may be, and preferably are, given an air-run after the treatment with the mineral acid or acid ester. After the air-run, in order to avoid destruction of the products consequent upon prolonged contact with the acidic substances, the materials may be freed therefrom, for example by washing with water alone or with water containing alkali or base. As indicated above the concentration of the baths, either. precipitating bath or subsequent treatment bath, should be adjusted to avoid a deleterious .degree of hydrolysis of the cellulose ester or ether. It is also found that for each acid or acid ester there exists a range of concentration within which stable spinning may be obtained. As the concentration of the mineral acid, and particularly sulphuric acid, in the precipitating bath or subsequent treatment bath is increased or as the time of immersion in the bath is increased, the products tend to become, progressively dull and may, if the concentration be carried sulficiently high or the time of immersion increased sufliciently, become straw-like to the touch. This latter possibility is of advantage in the production of ribbons where it is frequently desirable that the products should have this property. WVhile the stability of spinning and the hydrolysis of the cellulose ester or ether is dependent upon the concentration used, it is also dependent upon the speed of spinning and upon the time of immersion in the bath, so that with higher speeds of spinning or with shorter lengths of immersion, the concentration in the bath may be increased. It is preferable to use sufficiently high acid concentrations to avoid the production of precipitated opaque products. For example in order to obtain clear products concentrations of sulphuric acid below 20% should be avoided.
In order to moderate or to render more uniform the action of the mineral acid, additions, for example of glycerine, glucose or other sugars, alcohols or sulphonated oils, may be made to the baths. Furthermore, if
desired, in order to increase the stability of spinning, solvents or latent solvents may be added to the baths as described in U. S. Patent Specification No. 1,467,493. Similar additions may, if desired, be made to acid ester baths. Such solvents or additions preferably have no action on the mineral acids or acid esters.
The filaments, yarns or ribbons may be spun under tension according to the present invention, or if the mineral acid or acid ester be contained in a subsequent treatment bath, such treatment may take place under tension or not, or alternatively the products after production or treatment may be stretched or may be dried under tension.
The following examples illustrate the invention but are not to be considered as limiting it in anyway i Example 1 i 4 A 20% acetone solution of cellulose acetate is spun at a speed of 20 metres per minute into a bath consisting of 32% aqueous sulphuric acid, the length of immersion being about 6 inches. On emerging from the bath the yarn is passed over a feed roller and thence into a bath containing dilute ammonia, after which it may be wound, for example on bobbins, or may be twisted or hanked. The hanks may be washed and dried under a slight tension. Yarns or threads consisting of filaments of good lustre, strength and appearance are thus obtained.
E mamp le 2 A 20% acetone solution of cellulose acetate is spun into a bath containing 40% aqueous sulphuric acid, the speed of spinning and the length of immersion being the same as in Example 1.
E trample 3 Filaments are spun as in Example 1, but using a precipitating bath consisting of 46% aqueous sulphuric acid. The filaments obtained are much duller than those obtained in Example 1.
E wample 4 A 30% acetone solution of cellulose acetate is spun at a rate of 3 metres per minute through jet orifices suitable for obtaining ribbons and having a width of about .07 millimetres, into a precipitating bath consisting of a 30% aqueous solution of sulphuric acid, the length of immersion being about 3 feet. The ribbon on leaving the acid bath is passed into a bath containing dilute ammonia and is then reeled whilst running in water. A clear strong straw-like ribbon is thus obtained.
E wample 5 A 25% acetone solution of cellulose acetate is spun at a speed of 25 metres per minute into a bath consisting of a aqueous solution of diacetone alcohol. On emerging from the bath the yarn is passed into a second bath consisting of a 32% aqueous solution of sulphuric acid. the length of immersion being about 6 inches. On emergence from this bath the yarn is thereafter treated as in Example 1.
In a similar manner products may be obtained by spinning into aqueous solutions of hydrochloric acid or phosphoric acid or other mineral acids or partially esterified polybasic mineral acids. The strength of the baths to be used for any given length of immersion and any given speed may be readily ascertained by experiment.
hat we claim and desire to secure by Letters Patent is 1. Process for the manufacture of artificial materials by wet spinning processes from solutions of cellulose derivatives in organic solvents, comprising subjecting the materials continuously With their production to the action of a strong solution of a substance selected from the group consisting of strong mineral acids and acid esters of strong mineral acids.
2. Process for the production of artificial materials by Wet spinning processes from solutions of cellulose derivatives in organic solvents, comprising extruding the solutions into a bath containmg a strong solution of a substance selected from the group consisting of mineral acids and acid esters of strong mineral acids.
3. Process for the production of artificial materials by wet spinning processes from solutions of cellulose acetate in organic solvents, comprising extruding the solutions into a bath containing a strong solution of a substance selected from the group consisting of mineral acids and acid esters of strong mineral acids.
4. Process for the manufacture of artificial materials by Wet spinning processes from solutions of cellulose derivatives in organic solvents, comprising subjecting the materials continuously with their production to the action of strong aqueous sulphuric acid.
5. Process for the manufacture of artificial materials by Wet spinning processes from solutions of cellulose derivatives in organic solvents, characterized in that the materials are extruded into a coagulating medium and thereafter treated with a strong solution of a substance selected from the group consisting of a strong mineral acid and acid esters of strong mineral acids.
6. Process for the manufacture of artificial materials by wet spinning processes from solutions of cellulose acetate in organic solvents, characterized in that the materials are extruded into a coagulating medium and thereafter treated With a strong solution of a substance selected from the group consisting of a strong mineral acid and acid esters of strong mineral acids.
7. Process for the manufacture of artificial materials by Wet spinning processes from solutions of cellulose derivatives in organic solvents, comprising subjecting the materials continuously with their production to the action of a strong solution of a substance selected from the group consisting of strong mineral acids and acid esters of strong mineral acids, and thereafter washing the materials.
ln testimony whereof we have hereunto subscribed our names.
ROBERT PIERCE ROBERTS. REGINALD IVOR REID DEAN. LOUIS XVILFRED GREGORY.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB14503/29A GB334838A (en) | 1929-05-09 | 1929-05-09 | Improvements in the production of artificial threads, filaments, ribbons, films or the like from cellulose derivatives |
Publications (1)
Publication Number | Publication Date |
---|---|
US1903299A true US1903299A (en) | 1933-04-04 |
Family
ID=10042366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US431966A Expired - Lifetime US1903299A (en) | 1929-05-09 | 1930-02-27 | Production of artificial materials from cellulose derivatives |
Country Status (3)
Country | Link |
---|---|
US (1) | US1903299A (en) |
FR (1) | FR690772A (en) |
GB (1) | GB334838A (en) |
-
1929
- 1929-05-09 GB GB14503/29A patent/GB334838A/en not_active Expired
-
1930
- 1930-02-27 FR FR690772D patent/FR690772A/en not_active Expired
- 1930-02-27 US US431966A patent/US1903299A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
FR690772A (en) | 1930-09-25 |
GB334838A (en) | 1930-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2075888A (en) | Production of artificial filaments, threads, ribbons or the like by the dry spinning method | |
US1903299A (en) | Production of artificial materials from cellulose derivatives | |
US2025730A (en) | Manufacture of artificial threads, films, and other products by wet spinning processes from solutions of cellulose esters or ethers | |
US2081171A (en) | Manufacture of artificial materials | |
US2053766A (en) | Production of filaments, yarns, fabrics, and like materials | |
US2147642A (en) | Production of artificial filaments, films, and like materials | |
US2552598A (en) | Production of cellulose ester textile materials | |
US2702230A (en) | Cellulose acetate spinning process | |
US2004271A (en) | Production of artificial filaments, threads, ribbons, films, and the like | |
US2099005A (en) | Production or treatment of artificial filaments, threads, yarns, ribbons, and the like | |
US2145076A (en) | Method of preparing artificial threads | |
US2147641A (en) | Production of artificial filaments, films, and like materials | |
US2075027A (en) | Manufacture and treatment of artificial silk and like products | |
US1554801A (en) | Manufacture and application of fibers and fabrics | |
US1920188A (en) | Production of artificial materials | |
US3003846A (en) | Manufacture of artificial filamentary material | |
US2065664A (en) | Manufacture of articles from cellulose esters or ethers | |
US2004273A (en) | Production of cellulose derivative products | |
US2553483A (en) | Production of cellulose ester yarns suitable for conversion into staple fiber | |
US2070630A (en) | Manufacture of artificial filaments and other products containing organic derivatives of cellulose | |
US2112236A (en) | Manufacture of artificial filaments | |
US2025940A (en) | Production and treatment of textile and other materials made of or containing cellulose | |
US2086122A (en) | Production of artificial materials | |
US1883347A (en) | Process of making artificial filaments and product thereof | |
US2075430A (en) | Manufacture or treatment of artificial materials |